Au19Pt团簇性质及对肉桂醛选择性加氢机理研究

doi:10.7503/cjcu20160314

摘要/Abstract

摘要：

基于第一性原理密度泛函理论(DFT)方法研究了Pt掺杂的Au₁₉Pt团簇的结构稳定性、热力学稳定性和反应活性. 计算得出Au₁₉Pt-V团簇比Au₁₉Pt-S和Au₁₉Pt-E团簇的化学活性更强, 而热力学稳定性更低. 通过分析吸附能和电荷布居, 讨论了肉桂醛(CAL)在3类Au₁₉Pt团簇上的9种吸附构型. 计算结果表明, 当CAL以C=C双键平行吸附于Au₁₉Pt-V团簇的Pt原子上时, 其吸附能最大, CAL向团簇转移电子数最多, 吸附模型最稳定. 在最稳定吸附模型基础上探究了CAL选择性加氢的3类反应(1,2-加成反应、 3,4-加成反应和1,4-加成反应)的6条可能机理, 通过基元反应的过渡态搜索, 由反应热、反应能垒和构型的变化得到, CAL分子在Au₁₉Pt-V团簇上最有可能通过3,4-加成反应中的机理C进行, 即活泼H原子优先与C₃原子成键形成中间体MS3, 另一个H原子与中间体加成形成C₄—H键, 再经过过渡态TS34而形成最终产物苯丙醛(HCAL).

关键词: 密度泛函理论, 肉桂醛, Au19Pt团簇, 选择性加氢, 苯丙醛

Abstract:

Structural stability, thermodynamic stability and chemical reactivity of the bimetallic Au₁₉Pt clusters were investigated based on the framework of the relativistic density functional theory. It was calculated that Au₁₉Pt-V cluster was chemically more active than Au₁₉Pt-S and Au₁₉Pt-E clusters but thermodynamically less stable. To explore the most stable adsorption configuration, the adsorption behavior of a cinnamaldehyde on three types of bimetallic Au₁₉Pt cluster was studied via analyzing the adsorption energy and Mulliken charge. The calculation results indicate that a cinnamaldehyde molecule is preferably adsorbed on Pt site in Au₁₉Pt-V cluster with C=C, in which the adsorption configuration is the most stable. In that condition, the adsorption energy and the amount of charge transfer are maximum. Moreover, 6 possible mechanisms were investigated of three kinds of selective hydrogenation reaction(1,2-additive reaction, 3,4-additive reaction and 1,4-conjugate additive reaction) of cinnamaldehyde on Au₁₉Pt-V cluster, on the basis of the most stable adsorption configuration. Compared with the reaction energy, activation energy and configuration change of each elementary steps, it suggests that the most favorable way of the cinnamaldehyde on the Au₁₉Pt-V cluster would be through 3,4-additive reaction(mechanism C). The specific reaction pathway involved a C3 atom preferentially hydrogenating to generate MS3 intermediate, another H atom added to intermediate to take shape C4—H bond. Then the final product phenylpropyl aldehyde is forming through the transition state TS34.

Key words: Density functional theory, Cinnamaldehyde, Au19Pt cluster, Selective hydrogenation, Phenyl-propyl aldehyde

中图分类号:

O643

TrendMD:

曹勇勇, 蒋军辉, 倪哲明, 夏盛杰, 钱梦丹, 薛继龙. Au₁₉Pt团簇性质及对肉桂醛选择性加氢机理研究. 高等学校化学学报, 2016, 37(7): 1342.

CAO Yongyong, JIANG Junhui, NI Zheming, XIA Shengjie, QIAN Mengdan, XUE Jilong. Cluster Properties of Au₁₉Pt and Selective Hydrogenation Mechanism of Cinnamaldehyde on Au₁₉Pt Cluster Surface^†. Chem. J. Chinese Universities, 2016, 37(7): 1342.

图/表 12

Fig.1 Structure of cinnamaldehyde(CAL)

Fig.2 Optimized structures of Au20 and Au19Pt clusters (A) Au20; (B) Au19Pt-V; (C) Au19Pt-E; (D) Au19Pt-S.

Table 1 Relative bond length between the Pt atom and its nearest neighbor Au atom*

Pair	r_Au-Au/(r_Au+r_Pt)	r_Au-Pt/(r_Au+r_Pt)
Pt_E-Au_surface	1.018	0.977
Pt_E-A	1.070	1.021
Pt_E-A	0.968	0.958
Pt_V-Au_edge	0.985	0.946
Pt_S-Au_edge	1.018	1.008
Pt_S-Au_vertex	1.702	1.697

Table 2 Binding energy and d-band center of the pure Au20 and bimetallic tetrahedral Au19Pt clusters

System	ΔE_b/eV	E_{d-band center}/eV
Au₂₀	42.34	-3.24
Au₁₉Pt-S	43.42	-2.45
Au₁₉Pt-V	43.12	-2.39
Au₁₉Pt-E	43.40	-2.62

Fig.4 Optimized structure for the CAL molecule on the Au19Pt-E(A1—C1), Au19Pt-S(A2—C2) and Au19Pt-V(A3—C3) clusters(A1) PtE-σ(O); (A2) PtS-σ(O); (A3) PtV-σ(O); (B1) PtE-π(CO); (B2) PtS-π(CO); (B3) PtV-π(CO); (C1) PtE-π(CC); (C2) PtS-π(CC); (C3) PtV-π(CC).

Table 3 Adsorption energies(Eads) and Mulliken atomic charges(Q) of CAL on Au19Pt clusters

System	Final adsorption mode	E_ads/eV	Q_CAL/e
CAL/Au₁₉Pt-E	Pt_E-σ(O)	1.01	+0.185
	Pt_E-π(CO)	0.89	+0.138
	Pt_E-π(CC)	1.61	+0.220
CAL/Au₁₉Pt-S	Pt_S-σ(O)	0.66	+0.005
	Pt_S-π(CO)	0.82	+0.019
	Pt_S-π(CC)	0.74	+0.221
CAL/Au₁₉Pt-V	Pt_V-σ(O)	1.28	+0.113
	Pt_V-π(CO)	1.31	+0.270
	Pt_V-π(CC)	1.87	+0.272

Fig.5 Reaction mechanisms of CAL partial selective hydrogenation on Au19Pt-V cluster

Table 4 Activation energy(Ea) and reaction energy(ΔE) of possible six main reactions of CAL on Au19Pt cluster

Mechanism	Step	Reaction	E_a/eV	ΔE/eV
H₂ dissociation		H₂→H^+H^	0.99	-0.55
A	A(1)	CAL^+H^→MS1^*	0.51	0.17
	A(2)	MS1^+H^→COL^+	1.75	0.15
B	B(1)	CAL^+H^→MS2^*	3.97	1.12
	B(2)	MS2^+H^→COL^+	0.48	0.05
C	C(1)	CAL^+H^→MS3^*	1.08	0.33
	C(2)	MS3^+H^→HCAL^+	0.65	0.71
D	D(1)	CAL^+H^→MS4^*	1.38	1.03
	D(2)	MS4^+H^→HCAL^+	0.36	0.73
E	E(1)	CAL^+H^→MS1^*	0.51	0.17
	E(2)	MS1^+H^→ENOL^+	2.09	1.28
F	F(1)	CAL^+H^→MS4^*	1.38	1.03
	F(2)	MS4^+H^→ENOL^+	4.20	1.41

Fig.6 Simulation reaction process of mechanisms A and B(A) and energy diagrams of COL formation(B) a. Mechanism A; b. mechanism B.

Fig.7 Simulation reaction process of mechanisms C and D(A) and energy diagrams of HCAL formation(B) a. Mechanism C; b. mechanism D.

Fig.8 Simulation reaction process of mechanisms E and F(A) and energy diagrams of ENOL formation(B) a. Mechanism E; b. mechanism F.

Fig.9 Energy change of mechanisms A(a), C(b) and E(c) on Au19Pt-V cluster

参考文献 33

[1]	Lee J. D., Christopher M. A., Parlett1 N. S., Scientific Reports,2015, 5(9426), 1—7
[2]	Kolodziej M., Drelinkiewicz A., Lalik E., Gurgul J., Duraczynska D., Kosydar R., Applied Catalysis A: General,2016, 515, 60—71
[3]	Karl R., Kahsar D. K., Schwartz J., Will M., J. Am. Chem. Soc., 2014, 136, 520—526
[4]	Fang C., Chen Y. J., Mao B., Zhao J., Jiang Y. F., Zhao S. L., Ma J., Chem. J. Chinese Universities,2015, 36(1), 124—130(方超, 陈亚君, 毛卉, 赵俊, 蒋云福, 赵仕林, 马骏. 高等学校化学学报, 2015, 36(1), 124—130)
[5]	Li H., Ma C.J., Li H. X., Acta Chimica Sinica, 2006, 24, 1947—1953(李辉, 马春景, 李和兴. 化学学报, 2006, 24, 1947—1953)
[6]	Xue Q. Q., Karine P., Pierre L., Philippe S., Dalton Trans., 2014, 43, 9283—9295
[7]	Haeck J.D., Veldeman N., J. Phys.Chem. A, 2011, 115, 2103—2109
[8]	Qian H., Jiang D., Gayathri C., J. Am. Chem. Soc., 2012, 134, 16159—16162
[9]	Cheng L., Xiao Y. K., Zhi W. L., J. Phys. Chem. A,2011, 115, 9273—9281
[10]	Zhang X. D., Gao M. L., Wu D., Int. J. Mol. Sci., 2011, 12, 2972—2981
[11]	Yuan D. W., Wang Y., Zenga Z., J. Chem. Phys., 2005, 122, 114310
[12]	Mondal K., Ghanty T. K., Banerjee A., Mol. Phys., 2013, 111, 725—734
[13]	Sinfelt J. H., Accounts Chem. Res., 1987, 20, 134—136
[14]	Gholizadeh R., Yu Y. X., Appl. Surf. Sci., 2015, 357, 1187—1195
[15]	Liu T. T., Lu X., Zhang M. T., Chem. Res. Chinese Universities,2014, 30(4), 656—660
[16]	Pan W., Ma G. W., Yang X. D., Chem. J. Chinese Universities,2015, 36(2), 325—329(潘威, 马广文, 杨小东. 高等学校化学学报, 2015, 36(2), 325—329)
[17]	Tapan K. G., J. Phys. Chem. C, 2014, 118, 11935—11945
[18]	Anna V., Beletskaya D. P., Alexander F. S., J. Phys. Chem. A,2013, 117, 6817—6826
[19]	Ke Q. S., Yong C. H., Gui R. Z., ACS Catal., 2011, 1, 1336—1346
[20]	Yong C. H., Ke Q. S., Gui R. Z., Chem. Commun., 2011, 47, 1300—1302
[21]	Delley B., J. Phys. Chem. A, 2006, 110, 13632—13639
[22]	Chen W. K., Cao M. J., Liu S. H., Acta Phys-Chim Sinica,2005, 21, 903—908(陈文凯, 曹梅娟, 刘书红. 物理化学学报, 2005,21, 903—908)
[23]	Xiao X. C., Shi W., Ni Z. M., Zhang L. Y., Acta Phys-Chim Sinica,2015, 31, 885—892(肖雪春, 施炜, 倪哲明, 张连阳. 物理化学学报, 2015,31, 885—892)
[24]	Tao J., Yao Z.J., Xue F., Fundamentals of Material Science, Chemical Industry Press, 2006, 50—51
	(陶杰, 姚正军, 薛烽. 化学工业出版社, 2006, 50—51)
[25]	Ham H. C., Hwang G. S., Han J., Nam S. W., Lim T. H., J. Phys. Chem. C,2010, 114, 14922—14928
[26]	Morrow B. H., Resasco D. E., Striolo A., Nardelli M. B., J. Phys. Chem. C,2011, 115, 5637—5647
[27]	Diego C. A., Maria P. O., Luis S., J. Phys. Chem. A,2015, 119, 6909—6918
[28]	Delbecq D., Sautet P., J. Catal., 1995, 152, 217—236
[29]	Mulliken R. S., J. Chem. Phys., 1955, 23, 1833—1840
[30]	Loffreda D., Delbecq F., Vigne F., Sautet P., J. Am. Chem. Soc., 2006, 128, 1316—1323
[31]	Shi W., Zhang L. Y., Ni Z. M., Xiao X. C., Xia S. J., RSC Advances,2014, 4, 27003—27012
[32]	Zhang L.Y., Jiang J. H., Shi W., Xia S. J., Ni Z. M., RSC Advances,2015, 5, 34319—34326
[33]	Jiang J. H., Xia S. J., Ni Z. M., Zhang L.Y., Chem. J. Chinese Universities,2016, 37(4), 693—700(蒋军辉, 夏盛杰, 倪哲明, 张连阳. 高等学校化学学报, 2016, 37(4), 693—700)

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Au₁₉Pt团簇性质及对肉桂醛选择性加氢机理研究

Cluster Properties of Au₁₉Pt and Selective Hydrogenation Mechanism of Cinnamaldehyde on Au₁₉Pt Cluster Surface^†

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